Ethyl 2-(3-benzoyl­thio­ureido)acetate

Hassan, I.N.; Yamin, B.M.; Kassim, M.B.

doi:10.1107/S1600536808024896

organic compounds

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ISSN: 2056-9890

Volume 64| Part 9| September 2008| Page o1727

doi:10.1107/S1600536808024896

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Ethyl 2-(3-benzoylthioureido)acetate

Ibrahim N. Hassan,^a Bohari M. Yamin ^a and Mohammad B. Kassim ^a ^*

^aSchool of Chemical Sciences and Food Technology, Universiti Kebangsaan Malaysia, 43600 Bangi Selangor, Malaysia
^*Correspondence e-mail: mbkassim@ukm.my

(Received 29 July 2008; accepted 2 August 2008; online 9 August 2008)

The title compound, C₁₂H₁₄N₂O₃S, adopts a cis–trans geometry of the thiourea group and is stabilized by intramolecular hydrogen bonds between the carbonyl O atoms and the H atom of the thioamide group and by a C—H⋯S interaction. Molecules are linked by two intermolecular hydrogen bonds (C—H⋯O and N—H⋯O), forming a one-dimensional chain parallel to the c axis.

Related literature

For related literature, see: Allen et al. (1987 ); Ngah et al. (2005 ); Yamin & Hassan (2004 ); Yamin & Yusof (2003 ).

Experimental

Crystal data

C₁₂H₁₄N₂O₃S
M_r = 266.31
Monoclinic, P 2₁ /c
a = 11.908 (4) Å
b = 7.795 (3) Å
c = 14.024 (5) Å
β = 95.600 (5)°
V = 1295.5 (8) Å³
Z = 4
Mo Kα radiation
μ = 0.25 mm⁻¹
T = 298 (2) K
0.46 × 0.36 × 0.22 mm

Data collection

Bruker SMART APEX CCD area-detector diffractometer
Absorption correction: multi-scan (SADABS; Bruker, 2000 ) T_min = 0.893, T_max = 0.947
6762 measured reflections
2537 independent reflections
1967 reflections with I > 2σ(I)
R_int = 0.021

Refinement

R[F² > 2σ(F²)] = 0.041
wR(F²) = 0.107
S = 1.05
2537 reflections
164 parameters
H-atom parameters constrained
Δρ_max = 0.20 e Å⁻³
Δρ_min = −0.23 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N2—H2⋯O1	0.86	1.95	2.633 (2)	135
N2—H2⋯O2	0.86	2.43	2.724 (2)	101
C9—H9B⋯S1	0.97	2.70	3.045 (2)	101
N1—H1⋯O2ⁱ	0.86	2.35	3.164 (2)	158
C2—H2A⋯O1ⁱ	0.93	2.51	3.298 (3)	143
Symmetry code: (i) $[x, -y+{\script{1\over 2}}, z+{\script{1\over 2}}]$ .

Data collection: SMART (Bruker, 2000); cell refinement: SAINT (Bruker, 2000); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: SHELXTL (Sheldrick, 2008); software used to prepare material for publication: SHELXTL, PARST (Nardelli, 1995 ) and PLATON (Spek, 2003 ).

Supporting information

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536808024896/at2606sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536808024896/at2606Isup2.hkl

checkCIF report

Comment top

Some thiourea derivatives of amino acids, such as 2-[3-(4-methoxbenzoyl) thioureido]-3-methylbutyric acid (Ngah et al., 2005), 3-[3-(4-methoxybenzoyl) thioureido]propanoic acid and (Ngah et al., 2005) and 2-(3-benzoylthioureido) ethanoic dimethyl sulfoxide solvate (II) (Ngah et al., 2005) have been synthesized and their structures have been reported. We are interested to synthesize a series of esters containing thiourea moiety by catalytic transesterification. The title compound, (I), is an ester of (II).

The molecule maintains the cis-trans geometry of the thiourea moiety (Fig. 1). The phenyl ring (C1—C6) and (S1/N1/N2/O1/C6/C7/C8/C9) fragments are each planar with maximum deviation of 0.031 (2)Å for C6 atom from the least square plane of the later. The dihedral angle between the two planes is 26.53 (8)°. The bond lengths and angles are in normal ranges (Allen et al., 1987). There are three intramolecular hydrogen bonds, N2—H2···O1, N2—H2···O2 and C9—H9B···S1. As a result, one pseudo-six-membered ring (N2/H2/O1/C7/N1/C8) and two pseudo-five-member ring (N2/H2/O2/C10/C9) and (C9/H9B/S1/C8/N2) are formed, respectively. In the crystal structure, the molecules are linked by N1—H1···O2 and C9—H9B···S1 intermolecular hydrogen bonds to form one dimensional chain along the c axis (Fig. 2).

Related literature top

For related literature, see: Allen et al. (1987); Ngah et al. (2005); Yamin & Hassan (2004); Yamin & Yusof (2003).

Experimental top

2-(3-Benzoylthioureido)ethanoic acid was prepared as reported (Ngah et al., 2005). 2.38 g (10 mmol) of 2-(3-benzoylthioureido)ethanoic acid and 2.45 g (10 mmol) of lanthanum chloride were refluxed in methanol for 17 h. The resulting solution was left for one day at room temperature. Recrystallization of the resulting solid from dichloromethane gave colourless crystals of (I) [yield: 70%]).

Computing details top

Data collection: SMART (Bruker, 2000); cell refinement: SAINT (Bruker, 2000); data reduction: SAINT (Bruker, 2000); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: SHELXTL (Sheldrick, 2008); software used to prepare material for publication: SHELXTL (Sheldrick, 2008), PARST (Nardelli, 1995) and PLATON (Spek, 2003).

Figures top

	Fig. 1. The molecular structure of (I), with displacement ellipsods drawn at the 50% probability level.
	Fig. 2. A packing diagram of (I) viewed down the a axis. Hydrogen bonds are shown by dashed lines.

Ethyl 2-(3-benzoylthioureido)acetate top

Crystal data top

C₁₂H₁₄N₂O₃S	F(000) = 560
M_r = 266.31	D_x = 1.365 Mg m⁻³
Monoclinic, P2₁/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybc	Cell parameters from 2409 reflections
a = 11.908 (4) Å	θ = 1.7–26.0°
b = 7.795 (3) Å	µ = 0.25 mm⁻¹
c = 14.024 (5) Å	T = 298 K
β = 95.600 (5)°	Block, colourless
V = 1295.5 (8) Å³	0.46 × 0.36 × 0.22 mm
Z = 4

Data collection top

Bruker SMART APEX CCD area-detector diffractometer	2537 independent reflections
Radiation source: fine-focus sealed tube	1967 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.021
ω scans	θ_max = 26.0°, θ_min = 1.7°
Absorption correction: multi-scan (SADABS; Bruker, 2000)	h = −14→13
T_min = 0.893, T_max = 0.947	k = −9→9
6762 measured reflections	l = −16→17

Refinement top

Refinement on F²	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F² > 2σ(F²)] = 0.041	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.107	H-atom parameters constrained
S = 1.06	w = 1/[σ²(F_o²) + (0.0476P)² + 0.3616P] where P = (F_o² + 2F_c²)/3
2537 reflections	(Δ/σ)_max < 0.001
164 parameters	Δρ_max = 0.20 e Å⁻³
0 restraints	Δρ_min = −0.23 e Å⁻³

Crystal data top

C₁₂H₁₄N₂O₃S	V = 1295.5 (8) Å³
M_r = 266.31	Z = 4
Monoclinic, P2₁/c	Mo Kα radiation
a = 11.908 (4) Å	µ = 0.25 mm⁻¹
b = 7.795 (3) Å	T = 298 K
c = 14.024 (5) Å	0.46 × 0.36 × 0.22 mm
β = 95.600 (5)°

Data collection top

Bruker SMART APEX CCD area-detector diffractometer	2537 independent reflections
Absorption correction: multi-scan (SADABS; Bruker, 2000)	1967 reflections with I > 2σ(I)
T_min = 0.893, T_max = 0.947	R_int = 0.021
6762 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.041	0 restraints
wR(F²) = 0.107	H-atom parameters constrained
S = 1.06	Δρ_max = 0.20 e Å⁻³
2537 reflections	Δρ_min = −0.23 e Å⁻³
164 parameters

Special details top

Geometry. All e.s.d.'s (except the e.s.d. in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell e.s.d.'s are taken into account individually in the estimation of e.s.d.'s in distances, angles and torsion angles; correlations between e.s.d.'s in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell e.s.d.'s is used for estimating e.s.d.'s involving l.s. planes.

Refinement. Refinement of F² against ALL reflections. The weighted R-factor wR and goodness of fit S are based on F², conventional R-factors R are based on F, with F set to zero for negative F². The threshold expression of F² > σ(F²) is used only for calculating R-factors(gt) etc. and is not relevant to the choice of reflections for refinement. R-factors based on F² are statistically about twice as large as those based on F, and R- factors based on ALL data will be even larger.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å²) top

	x	y	z	U_iso*/U_eq
S1	0.36516 (4)	0.11910 (9)	0.60927 (4)	0.0632 (2)
O1	0.01958 (11)	0.1765 (2)	0.44591 (9)	0.0615 (4)
O2	0.21706 (12)	0.0629 (2)	0.25554 (10)	0.0657 (4)
O3	0.37578 (11)	−0.0928 (2)	0.25994 (9)	0.0626 (4)
N1	0.15088 (12)	0.2028 (2)	0.57452 (10)	0.0454 (4)
H1	0.1613	0.2428	0.6319	0.055*
N2	0.22969 (13)	0.0690 (2)	0.45050 (11)	0.0506 (4)
H2	0.1650	0.0821	0.4183	0.061*
C1	−0.03537 (15)	0.2974 (3)	0.68490 (13)	0.0482 (5)
H1A	0.0242	0.2412	0.7196	0.058*
C2	−0.11815 (16)	0.3747 (3)	0.73213 (14)	0.0540 (5)
H2A	−0.1145	0.3696	0.7986	0.065*
C3	−0.20575 (16)	0.4590 (3)	0.68161 (15)	0.0545 (5)
H3	−0.2610	0.5118	0.7139	0.065*
C4	−0.21224 (16)	0.4658 (3)	0.58254 (15)	0.0564 (5)
H4	−0.2714	0.5237	0.5483	0.068*
C5	−0.13077 (15)	0.3864 (3)	0.53472 (14)	0.0506 (5)
H5	−0.1361	0.3887	0.4681	0.061*
C6	−0.04087 (14)	0.3032 (2)	0.58545 (12)	0.0417 (4)
C7	0.04366 (15)	0.2218 (3)	0.52873 (13)	0.0455 (4)
C8	0.24393 (15)	0.1270 (2)	0.53931 (13)	0.0438 (4)
C9	0.31818 (16)	−0.0154 (3)	0.40544 (13)	0.0530 (5)
H9A	0.3234	−0.1342	0.4260	0.064*
H9B	0.3898	0.0398	0.4250	0.064*
C10	0.29539 (15)	−0.0079 (3)	0.29841 (13)	0.0477 (5)
C11	0.36926 (19)	−0.1060 (4)	0.15628 (15)	0.0689 (6)
H11A	0.3349	−0.0035	0.1270	0.083*
H11B	0.3236	−0.2041	0.1345	0.083*
C12	0.4835 (2)	−0.1258 (5)	0.1294 (2)	0.1037 (11)
H12A	0.5247	−0.0212	0.1424	0.155*
H12B	0.4808	−0.1518	0.0623	0.155*
H12C	0.5205	−0.2176	0.1658	0.155*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
S1	0.0420 (3)	0.0982 (5)	0.0482 (3)	0.0141 (3)	−0.0011 (2)	−0.0037 (3)
O1	0.0460 (8)	0.0913 (11)	0.0454 (8)	0.0093 (7)	−0.0038 (6)	−0.0176 (7)
O2	0.0519 (8)	0.0904 (12)	0.0549 (8)	0.0172 (8)	0.0059 (7)	0.0103 (8)
O3	0.0517 (8)	0.0912 (11)	0.0451 (8)	0.0174 (8)	0.0064 (6)	−0.0090 (7)
N1	0.0373 (8)	0.0613 (11)	0.0374 (8)	0.0036 (7)	0.0020 (6)	−0.0044 (7)
N2	0.0394 (8)	0.0679 (11)	0.0440 (9)	0.0061 (8)	0.0027 (7)	−0.0091 (8)
C1	0.0392 (9)	0.0605 (13)	0.0441 (10)	0.0027 (9)	−0.0004 (8)	0.0007 (9)
C2	0.0479 (11)	0.0718 (14)	0.0423 (10)	−0.0006 (10)	0.0049 (8)	−0.0038 (10)
C3	0.0431 (10)	0.0649 (14)	0.0567 (12)	0.0026 (10)	0.0109 (9)	−0.0082 (10)
C4	0.0413 (10)	0.0695 (14)	0.0582 (12)	0.0115 (10)	0.0030 (9)	0.0066 (10)
C5	0.0427 (10)	0.0663 (14)	0.0420 (10)	0.0027 (10)	0.0005 (8)	0.0031 (9)
C6	0.0340 (9)	0.0472 (11)	0.0437 (9)	−0.0023 (8)	0.0020 (7)	−0.0009 (8)
C7	0.0403 (9)	0.0530 (12)	0.0425 (10)	−0.0013 (8)	0.0000 (8)	−0.0003 (8)
C8	0.0403 (9)	0.0491 (11)	0.0426 (10)	0.0020 (8)	0.0069 (8)	0.0048 (8)
C9	0.0486 (11)	0.0632 (14)	0.0479 (11)	0.0103 (10)	0.0078 (9)	−0.0017 (10)
C10	0.0407 (10)	0.0548 (12)	0.0480 (10)	−0.0036 (9)	0.0075 (8)	−0.0022 (9)
C11	0.0648 (13)	0.0956 (18)	0.0464 (12)	0.0088 (13)	0.0057 (10)	−0.0100 (12)
C12	0.0712 (17)	0.176 (3)	0.0673 (16)	0.0198 (19)	0.0224 (13)	−0.0087 (19)

Geometric parameters (Å, º) top

S1—C8	1.6656 (19)	C3—C4	1.385 (3)
O1—C7	1.221 (2)	C3—H3	0.9300
O2—C10	1.194 (2)	C4—C5	1.379 (3)
O3—C10	1.322 (2)	C4—H4	0.9300
O3—C11	1.452 (2)	C5—C6	1.387 (3)
N1—C7	1.380 (2)	C5—H5	0.9300
N1—C8	1.388 (2)	C6—C7	1.485 (3)
N1—H1	0.8600	C9—C10	1.500 (3)
N2—C8	1.320 (2)	C9—H9A	0.9700
N2—C9	1.439 (2)	C9—H9B	0.9700
N2—H2	0.8600	C11—C12	1.455 (3)
C1—C2	1.379 (3)	C11—H11A	0.9700
C1—C6	1.390 (2)	C11—H11B	0.9700
C1—H1A	0.9300	C12—H12A	0.9600
C2—C3	1.370 (3)	C12—H12B	0.9600
C2—H2A	0.9300	C12—H12C	0.9600

C10—O3—C11	118.29 (16)	O1—C7—C6	121.65 (16)
C7—N1—C8	127.91 (15)	N1—C7—C6	116.19 (15)
C7—N1—H1	116.0	N2—C8—N1	116.61 (15)
C8—N1—H1	116.0	N2—C8—S1	124.54 (14)
C8—N2—C9	122.58 (15)	N1—C8—S1	118.83 (14)
C8—N2—H2	118.7	N2—C9—C10	110.66 (16)
C9—N2—H2	118.7	N2—C9—H9A	109.5
C2—C1—C6	120.11 (17)	C10—C9—H9A	109.5
C2—C1—H1A	119.9	N2—C9—H9B	109.5
C6—C1—H1A	119.9	C10—C9—H9B	109.5
C3—C2—C1	120.33 (18)	H9A—C9—H9B	108.1
C3—C2—H2A	119.8	O2—C10—O3	125.96 (18)
C1—C2—H2A	119.8	O2—C10—C9	125.28 (18)
C2—C3—C4	120.14 (18)	O3—C10—C9	108.75 (16)
C2—C3—H3	119.9	O3—C11—C12	107.9 (2)
C4—C3—H3	119.9	O3—C11—H11A	110.1
C5—C4—C3	119.86 (18)	C12—C11—H11A	110.1
C5—C4—H4	120.1	O3—C11—H11B	110.1
C3—C4—H4	120.1	C12—C11—H11B	110.1
C4—C5—C6	120.32 (18)	H11A—C11—H11B	108.4
C4—C5—H5	119.8	C11—C12—H12A	109.5
C6—C5—H5	119.8	C11—C12—H12B	109.5
C5—C6—C1	119.22 (17)	H12A—C12—H12B	109.5
C5—C6—C7	117.04 (16)	C11—C12—H12C	109.5
C1—C6—C7	123.72 (16)	H12A—C12—H12C	109.5
O1—C7—N1	122.16 (17)	H12B—C12—H12C	109.5

C6—C1—C2—C3	−0.6 (3)	C5—C6—C7—N1	154.41 (18)
C1—C2—C3—C4	0.6 (3)	C1—C6—C7—N1	−26.8 (3)
C2—C3—C4—C5	0.5 (3)	C9—N2—C8—N1	−178.79 (17)
C3—C4—C5—C6	−1.5 (3)	C9—N2—C8—S1	2.7 (3)
C4—C5—C6—C1	1.5 (3)	C7—N1—C8—N2	1.6 (3)
C4—C5—C6—C7	−179.66 (19)	C7—N1—C8—S1	−179.77 (16)
C2—C1—C6—C5	−0.5 (3)	C8—N2—C9—C10	−158.69 (18)
C2—C1—C6—C7	−179.21 (19)	C11—O3—C10—O2	−1.2 (3)
C8—N1—C7—O1	−3.0 (3)	C11—O3—C10—C9	178.55 (19)
C8—N1—C7—C6	177.93 (17)	N2—C9—C10—O2	2.4 (3)
C5—C6—C7—O1	−24.7 (3)	N2—C9—C10—O3	−177.34 (17)
C1—C6—C7—O1	154.1 (2)	C10—O3—C11—C12	153.0 (2)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N2—H2···O1	0.86	1.95	2.633 (2)	135
N2—H2···O2	0.86	2.43	2.724 (2)	101
C9—H9B···S1	0.97	2.70	3.045 (2)	101
N1—H1···O2ⁱ	0.86	2.35	3.164 (2)	158
C2—H2A···O1ⁱ	0.93	2.51	3.298 (3)	143

Symmetry code: (i) x, −y+1/2, z+1/2.

Experimental details

Crystal data
Chemical formula	C₁₂H₁₄N₂O₃S
M_r	266.31
Crystal system, space group	Monoclinic, P2₁/c
Temperature (K)	298
a, b, c (Å)	11.908 (4), 7.795 (3), 14.024 (5)
β (°)	95.600 (5)
V (Å³)	1295.5 (8)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	0.25
Crystal size (mm)	0.46 × 0.36 × 0.22

Data collection
Diffractometer	Bruker SMART APEX CCD area-detector diffractometer
Absorption correction	Multi-scan (SADABS; Bruker, 2000)
T_min, T_max	0.893, 0.947
No. of measured, independent and observed [I > 2σ(I)] reflections	6762, 2537, 1967
R_int	0.021
(sin θ/λ)_max (Å⁻¹)	0.617

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.041, 0.107, 1.06
No. of reflections	2537
No. of parameters	164
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.20, −0.23

Computer programs: SMART (Bruker, 2000), SAINT (Bruker, 2000), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), SHELXTL (Sheldrick, 2008), PARST (Nardelli, 1995) and PLATON (Spek, 2003).

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N2—H2···O1	0.86	1.95	2.633 (2)	135
N2—H2···O2	0.86	2.43	2.724 (2)	101
C9—H9B···S1	0.97	2.70	3.045 (2)	101
N1—H1···O2ⁱ	0.86	2.35	3.164 (2)	158
C2—H2A···O1ⁱ	0.93	2.51	3.298 (3)	143

Symmetry code: (i) x, −y+1/2, z+1/2.

Acknowledgements

The authors thank Universiti Kebangsaan Malaysia for providing the facilities and the Ministry of Science, Technology and Innovation for the research fund No. UKM-ST-01FRGS0016–2006.

References

Allen, F. H., Kennard, O., Watson, D. G., Brammer, L., Orpen, A. G. & Taylor, R. (1987). J. Chem. Soc. Perkin Trans. 2, pp. S1–19. CrossRef Web of Science Google Scholar
Bruker (2000). SADABS, SMART and SAINT. Bruker AXS Inc., Madison, Wisconsin, USA. Google Scholar
Nardelli, M. (1995). J. Appl. Cryst. 28, 659. CrossRef IUCr Journals Google Scholar
Ngah, N., Shah, N. M., Kassim, M. B. & Yamin, B. M. (2005). Acta Cryst. E61, o1910–o1912. Web of Science CSD CrossRef IUCr Journals Google Scholar
Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. Web of Science CrossRef CAS IUCr Journals Google Scholar
Spek, A. L. (2003). J. Appl. Cryst. 36, 7–13. Web of Science CrossRef CAS IUCr Journals Google Scholar
Yamin, B. M. & Hassan, I. N. (2004). Acta Cryst. E60, o2513–o2514. Web of Science CSD CrossRef IUCr Journals Google Scholar
Yamin, B. M. & Yusof, M. S. M. (2003). Acta Cryst. E59, o151–o152. Web of Science CSD CrossRef CAS IUCr Journals Google Scholar